Multi-purpose cleaner-germicide-deodorizer composition



United States Patent 3,118,842 MULTI-PURPQSE CLEANE -GERMECEDE- DEODGREZER COMPITIGN Eli D. Basset", China Lake, Calif, assiguor to Marveli Industries, Pasadena, "Calif, a partnership of California No Drawing. Filed. .luiy 13, 1959, Ser. No. 826,428 8 Claims. (Cl. 252-106) This invention relates to a unique type of multi-purpose cleaner germicide-deodorizer, more particularly it relates to a solution that can be used for cleaning, disinfecting, and deodorizing. It further relates to a composition both unique in composition and in its effectiveness.

Prior cleaning, disinfecting, and deodorizing solutions have been subject to the following disadvantages:

According to former procedures, the cleaning solutions have been used in the first operation and then the surface completely rinsed and freed of chemicals before a germicide or disinfectant could be applied to the surfaces because of antagonism set up between the alkalinity of the cleaners and the chemical activity of the germicide or disinfectant: e.g., types of quaternary ammonium compounds, and iodine or chlorine freeing compounds. The iodophors must be used at a pH below to be effective. The quaternary ammonium compounds, iodophors, and chlorine-freeing compounds are also characterized by a strong lingering odor that in many cases is objectionable, particularly around foods, where antagonisms are set up between fragrances.

Early development of dual-purpose cleaners were combinations of soap and phenolics, or pine oils; further modifications included substitution of synthetic detergents for all or part of the soap present.

To accomplish multi-purpose action, it has been necessary to first clean the surfaces with a soap or soap detergent combination, to completely neutralize the surface from the alkalinity or antagonism of the soap or soap detergent combination, to cover or flood the surface with a sanitizer or germicide and, lastly to rinse the surface free of sanitizer/germicide to minimize odor contamination.

Cleaner-sanitizers have also been made available by the use of a solvent to carry the sanitizing-germicidal agent or agents. This represents a hazard, however, because of the flammability of the solvent. This type of solution is also limited in its application because of irritations it can elicit on hands and because of the possible damage it may do to solvent-sensitive surfaces.

The necessity for germicidal action has recently hecome of major importance, particularly because of the ineffectiveness of the antibiotics to offer continued protection against many of the common bacteria, particularly the coagulate positive Staphylococcus aureus.

It is therefore an object of this invention to provide a cleaner-germicide-deodorizer that can simultaneously clean, disinfect, and deodorize in one operation.

It is a further object of this invention to combine all previous steps of cleaning, disinfecting, and deodorizing into one simple operation; thereby effecting multi-purpose operational cleaning.

It is a further object of this invention to provide a balance of nonionic and anionic detergents plus other surface active agents to effectively clean all surfaces in an efficient, safe manner.

It is a further object of this invention to not only clean and deodorize, but to disinfect and/ or sterilize surfaces being cleaned; the germicidal properties being effective by the solutions water-insoluble ingredients.

It is a further object of this invention to accomplish the deodorization by the solutions residual type of germicidal action in a very lasting manner.

It is a further object of this invention to accomplish the above in a safe, harmless manner using a solution that is actually beneficial to hands, surfaces, etc.

Other objectives of the invention are brought out in the further description of the process.

It has been found that the above and other objects can be accomplished by a solution containing:

From about five (5) to about twenty (20) percent of a nonionic surface active agent (polypropyleneglycolethylene oxide being a preferred type),

From about five (5) to about twenty (20) percent of an amphoteric type surface active agent (ethylene cycloimido, 1 alkyl (fatty acid), 2 hydroXy-ethylene sodium alcoholate, methylene sodium carboxylate being a preferred type).

From about two (2) to about eight (8) percent of an alkyl-aryl sulfonate.

From zero to about three (3) percent of an alkaline buffer (sodium carbonate being preferred), and

From about two-tenths (0.2) to about eight-tenths (0.8) percent of a chlorinated bisphenol (or bithionol) compound.

This invention is compounded upon the unique synergistic characteristics developed by the particular blending of the indicated type ingredients.

The invention is illustrated by the following examples which are illustrative of the invention but not limiting thereof.

Example I Composition: Percentage Polypropyleneglycol-ethylene oxide polymer (nonionic surface active agent), Pluronics L62 15.0 Ethylene cycloirnido, 1 alkyl (fatty acid),

2 hydroxyethylene sodium alcoholate, methylene sodium carboxylate (amphoteric type surface active agent), Miranol CM Conc. coconut derivative 10.0 Chlorinated bisphenol (Dichlorophene) 0.3 Water 74.7

Trademark of Wyandotte Chemical Corp., Wyandotte, Michigan.

Trademark of Miranol Chemical Co., Inc., Irvington, New Jersey.

The Dichlorophene compound is first solubilized in the Pluronics L62 with constant stirring on a water bath, keeping the temperature of the solution below F. to minimize decomposition. Upon complete solubilization of the Dichlorophene in the Pluronics L62, the solution is removed from the Water bath and with continued stirring, the Miranol CM Conc. and water are added. Coloring and aromatic fragrances may or may not be added as desired. There is only a faint pleasant odor from the amphoteric surface active agent present.

This solution has been used in practice with concentrations as low as one ounce per gallon and has demonstrated superior cleaning, disinfecting, and deodorizing properties.

3 Example 11 Composition: Percentage Polypropyleneglycol-ethylene oxide polymer (nonionic surface active agent), Pluronics L64 15.0 Ethylene cycloimido, 1 alkyl (fatty acid),

2 hydroxyethylene sodium alcoholate, methylene sodium carboxylate (amphoteric type surface active agent), Miranol SM Conc. capric derivative 10.0 Chlorinated bisphenol (hexachlorophene) 0.6 Alkylaryl sulfonate synthetic detergent (Kreelon 4G) 5.0 Sodium carbonate 2.0 Water 67.4

Tradeinark of Wyandotte Chemical Corp, Wyandottc, Michigan.

Trademark of Mlranol Chemical Co., Inc., Irvington, New Jersey.

Example 111 Composition: Percentage Polypropyleneglycol-ethylene oxide polymer (non-ionic surface active agent), Fluronics F68 1 10.0 Lauroylcycloimidinium-l ethoxy-ethionic acidl-ethionic acid, disodinm salt (amphoteric type surface active agent) Miranol CZM Conc. 15.0 2,2-thiobis (4,6-dichlorophenol), Actarner bithionol 0.4 Alkylaryl sulfonate synthetic detergent (Krcelon 4G) 3.0 Water 71.6 100.0

Inc., Irrington,

St. Louis,

This compound has the following structural formula:

/CI'I2 Ifil CH2 CIIzCHzOCIIgCOONa CnHzaC N OH CHzC O ONa In Examples II and III, the chlorinated bisphenol or the bithionol compound is similarly solubilized in the nonionic surface active agent in the manner described in Example I, and the remaining ingredients are added with continued stirring. Color and/or fragrances may be added, as in Example I.

The Pluronics L64 and F68 described in Examples II and III have a greater solubilizing action for the chlorinatcd bisphenol (or bithionol) compounds because of a higher ratio of polypropylene oxide in their chemical structures.

The alkylaryl sulfonates and the sodium carbonates, although not essential in the teachings of the invention, have advantages in buffering and in controlling the alkalinity of the solution in the pH range of 8.0 to 9.5; thereby assuring complete germicidal effectiveness of the chlorinated bisphenols (or bithionols).

The critical limits of the percentage ranges of the composition are as follows:

Percent Polypropyleneglycol-ethylene oxide polymer (nonionic surface active agent) 5 to Ethylene cycloimido; 1 alkyl, 2 hydroxyethylene sodium alcoholate, methylene sodium carboxylate (amphoteric surface active agent) 5 to 20 Percent Alkylaryl sulfonatc 2 to 8 Sodium carbonate 0 to 3 Chlorinated bisphenol (or bithionol compounds) 0.2 to 0.8

The polypropylencgiycol-ethylene oxide polymer, a noniornc surface active agent, combines excellent stability, detergency and emulsifying properties within its own molecular weight structure. As the molecular weight of the polypropyleneglycol is increased, the glycol passes from a water soluble to a relatively water-insoluble compound. At higher molecular weights, it is sufficiently Water-insoluble to be a suitable hydrophobic base for a nonionic surface active agent. The surface activity is obtained by condensing ethylene oxide on the polypropylene base. These polymers are relatively free of taste and have an unusually low order of toxicity and irritation. They are extremely stable in acids, alkalics, and most metallic ions; are effective in lowering interfacial tension, and have a high suspending power. Their unusually high molecular weights (2000 to 8000) make possible many of the above enumerated properties.

The formulas for the preferred polyproyleneglycolethylene oxide polymers vary between:

I'IO 6 (CSIIGO 26 6P1 ronics L62, and

HO(C H O) (C H O) (C l-I O) H representing Pluronics F68.

The properties of the Pluronics L64 range between those of L62 and F68. The molecular weights of Pluronics L62, L64 and F68 are 2500, 2900 and 8000 respectively.

Not only do these polymers provide excellent detergent cleaning properties and suds control by the chain length of the ethylene oxide grouping in the molecule, but they also have the very important property of solubilizing the chlorinated bisphenol (or bithionol) type compounds; thus eliminating the necessity for a polar, volatile solvent to solubilize the chlorinated bisphenol (or bithionol) type compounds.

Remainder.vater.

The amphoteric cycloimido type compounds preferred in the disclosure have the following generic chemical structure:

representing Plu- R representing the fatty acid radical (coconut, cnpric, stearic, etc).

CHzCHeONa Its particular type structure, containing carboxylates and alcoholates, make it extremely effective as a detergent-cleaner (the carboxyl group is generally recognized to be one of the major contributors to soaps detcrgency on cotton); its mildly quaternary ammonium grouping gives it germicidal properties in solution without the associated strong ammoniacal odor; its amphoteric properties make it effective as an excellent cleaner throughout the pH range (1 to 14). The amphoteric properties are derived by virtue of the quaternary ammonium grouping on the one hand, and the stronger sodium carboxyl grouping on the other.

Sulfo groups or ethylene oxide groups do not provide adequate detergency. The amide carboxylates are incapable of providing sufiicient sequestration to make the product impervious to the hardness effects of water. The cycloimidine in the compounds herein described, however solves the sequestration problem by their chelating characteristics. These cycloimido type compounds are soluble in acid as well as in alkaline solutions.

The Miranol CM Conc. (coconut derivative), disclosed in Example I, is particularly outstanding for its germicidal and deodorizing properties, its non-toxicity and non-irritating qualities, and its excellent, stable foaming and outstanding detergency characteristics.

The Miranol SM Conc. (capric derivative), disclosed in Example II, is outstanding for its good spreading properties (low surface tension), its low penetrating powers,

lackofi odor, and its mildness.

The Miranol C2M Cone. (dicarboxylic analog of the CM ConcI), disclosed in Example III, is especially recommended for formulations where complete absence of irritation is desirable (intradermal injection tests prove it better than olive oil Castile soap). It is also characterized by its providing profuse and instant flash foaming to solutions and for forming crystal clear products by its exceptional temperature stability.

The sodium alkylaryl sulfonates are synthetic detergents, broadly classified as surface active agents with the following properties: wetting, penetrating, spreading, emulsifying, dispersing or peptizing, surface tension lowering, cleaning, and detergency. They function effectively in acid, alkaline or neutral solutions, in hard or soft waters, alone, or combined in solutions and dry mixes with a large number of other chemicals.

The type disclosed in Examples II and III (Kreelon 4G) is a sodium salt of a sulfonated alkyl (straight chain) benzene, specifically, it is sodium dodecylbenzenesulfonate. It is soluble in waters of hardness from to 400 parts per million (expressed as calcium carbonate). By its detergent action it decreases interfacial tension, solubilizes soil in the detergent solution, emulsifies and deflocculates, and prevents redeposition. It will not oxidize and turn rancid if retained on fabrics due to inadequate rinsing.

Kreelon 46 has excellent detersive qualities, rinsibility, and the property of forming clear solutions. It is elfective in either acid or alkaline solutions and holds up well in hot alkaline solutions under both direct and reverse current. Though mild and neutral, this anionic surface agent has pronounced surface activity, making it a powerful detergent.

The sodium carbonate disclosed in Example III, offers buffering properties to hold the solution on the slightly alkaline side (pH 8.0 to 9.5), where the germicidal effectiveness of the chlorinated bisphenols (or bithionols) is greatest.

The chlorinated bisphenol and chlorinated bithionol type compounds by their relationship to phenol have already established a background as effective germicides. They are characterized, however, by their extremely low rder of toxicity. In skin application tests they do not sensitize and fatigue normal human skin. Their effectiveness comes about by their inhibiting the growth and reproduction of susceptible bacteria. Since the reproductive cycle of bacteria can be short, effective inhibition of growth rapidly decimates their number. Once reduction is effected, repopulation can take place only through the subsequent multiplication of survivors or by reinoculation followed by growth. Thus, reduction of bacterial count by anti-sepsis serves only a temporary purpose unless the antiseptic agent is reapplied frequently or can be kept in contact with the surfaces for relatively long periods of time.

For an agent to be effective in keeping surfaces com paratively germ free:

It must inhibit growth of bacteria and must not be activated by any component of the solution (or preparation) in which it is used (organic vehicles, protein, fats, etc.).

It must be effective in low concentrations.

Its activity must persist long after application (insoluble in water).

It must have residual effectiveness which will be enhanced upon moistening.

It must have low toxicity, it must be stable, it must be compatible in formulations.

Many publications have indicated the effectiveness of chlorinated bisphenol (or bithionol compounds) as antibacterial agents, germicides, and fungicides. The Repeated Insult Test of Draize and Shelanski in the Proceedings of the Scientific Section of the Toilet Goods Association, No. 19, May 1953, a critical procedure designed to disclose irritating and skin sensitizing properties, indicated that chlorinated bisphenols and chlorinated bithionols are not primary irritants, sensitizers, or skinfatiguing agents.

The dichlorophene (or 2,2'-methylenebis-(4-chlorophenol) disclosed in Example I, is particularly elfective as a fungicide and bactericide. The hexachlorophene (or 2,2'-methylenebis-(3,4,6-trichlorophenol)), disclosed in Example II, has demonstrated its extreme effectiveness against Staphylococcus aureus (or Micrococcus pyogenes variety aureus), as well as against gram-positive and gramnegative bacteria in field tests under actual use conditions. The Actamer bithionol (or 2,2-thiobis (4,-6-dichlorophenol)), disclosed in Example III, has proved equally effective in the same tests. It is characterized by its long residual effectiveness.

While the invention has been illustrated by specific examples within the specified percentage ranges of ingredients it is by no means limited thereto, but compositions generally within the percentage ranges given are operative for the purposes of the invention.

Obviously many modifications and variations of the present invention are possible in the light of the above teachings. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than specifically described.

What is claimed is:

1. A cleaner-germicide-deodorizer composition in the form of a stable water-base solution consisting essentially of, by weight, from about 5 to about 20 percent of a polypropylene-glycolethylene oxide condensation product having a molecular weight range from about 2000 to about 8000 and having the formula where x is a number between 6 and 72, inclusive; from about 5 to about 20 percent of an amphoteric type surface active agent from the class consisting of compounds having the structural formula wherein R is a hydrocarbon radical from the class consisting of coconut, capric and stearic radicals, and the compound having the structural formula N om CHzCHzOCHgOOONa l/ C11HzsC- I\ OH CHzCOONa 7 from about 0.2 to about 0.8 percent of a compound from the class consisting of dichlorophene, hexachlorophone and 2,2'-thiobis 4,6-dichlorophenol; and the remainder Water.

2. The composition of claim 1 having a pH within the range of about 8.0 to about 9.5.

3. The composition of claim 1 in which Water is replaced by sodium carbonate in an amount up to about 3 percent.

4. The composition of claim 1 in which water is replaced by sodium dodecylbenzene sulfonate in an amount from about 2 to about 8 percent.

5. The composition of claim 1 in Which the amphoteric type surface active agent is a compound having the structural formula 6. The composition of claim 1 in which the amphoteric type surface active agent is a compound having the structural formula CH2 CHzCHzONa.

7. The composition of claim 1 in which the amphoteric type surface active agent is a compound having the structural formula 8. The composition of claim 1 in which the amphoteric type surface active agent is a compound having the structural formula References Cited in the file of this patent UNITED STATES PATENTS 2,898,264 Weber Aug. 4, 1959 2,950,255 Goff Aug. 23, 1960 FOREIGN PATENTS 744,433 Great Britain Feb. 8, 1956 OTHER REFERENCES 

1. A CLEANER-GERMICIDE-DEODORIZER COMPOSITION IN THE FORM OF A STABLE WATER-BASE SOLUTION CONSISTING ESSENTIALLY OF, BY WEIGHT, FROM ABOUT 5 TO ABOUT 20 PERCENT OF A POLYPROPYLENE-GLYCOL-ETHYLENE OXIDE CONDENSATION PRODUCT HAVING A MOLECULAR WEIGHT RANGE FROM ABOUT 2000 TO ABOUT 8000 AND HAVING THE FORMULA 